van den Brand J, Blajiev O, Beentjes P C J, Terryn H, de Wit J H W
Netherlands Institute for Metals Research, Rotterdamseweg 137, 2628 AL Delft, The Netherlands.
Langmuir. 2004 Jul 20;20(15):6318-26. doi: 10.1021/la049456a.
The bonding of two types of ester group-containing molecules with a set of different oxide layers on aluminum has been investigated using infrared reflection absorption spectroscopy. The different oxide layers were made by giving typical surface treatments to the aluminum substrate. The purpose of the investigation was to find out what type of ester-oxide bond is formed and whether this is influenced by changes in the composition and chemistry of the oxide. The extent by which these bonded ester molecules resisted disbondment in water or substitution by molecules capable of chemisorption was also investigated. The ester groups were found to show hydrogen bonding with hydroxyls on the oxide surfaces through their carbonyl oxygens. For all oxides, the ester groups showed the same nu(C = O) carbonyl stretching vibration after adsorption, indicating very similar bonding occurs. However, the oxides showed differences in the amount of molecules bonded to the oxide surface, and a clear relation was observed with the hydroxyl concentration present on the oxide surface, which was determined from XPS measurements. The two compounds showed differences in the free to bonded nu(C = O) infrared peak shift, indicating differences in bonding strength with the oxide surface between the two types of molecules. The bonding of the ester groups with the oxide surfaces was found to be not stable in the presence of water and also not in the presence of a compound capable of chemisorption with the aluminum oxide surface.
利用红外反射吸收光谱法研究了两种含酯基分子与铝表面一系列不同氧化层的键合情况。通过对铝基板进行典型的表面处理来制备不同的氧化层。该研究的目的是确定形成了何种类型的酯 - 氧化物键,以及这是否受氧化物组成和化学性质变化的影响。还研究了这些键合的酯分子在水中抵抗解离或被能够化学吸附的分子取代的程度。发现酯基通过其羰基氧与氧化物表面的羟基形成氢键。对于所有氧化物,吸附后酯基显示出相同的ν(C = O)羰基伸缩振动,表明发生了非常相似的键合。然而,氧化物在与氧化物表面键合的分子数量上存在差异,并且观察到与通过XPS测量确定的氧化物表面存在的羟基浓度有明显关系。这两种化合物在自由态到键合态的ν(C = O)红外峰位移上存在差异,表明两种类型分子与氧化物表面的键合强度不同。发现酯基与氧化物表面的键合在有水存在时不稳定,在存在能够与氧化铝表面化学吸附的化合物时也不稳定。